Substituted cyanamides and their use as fungicides

ABSTRACT

New, substituted cyanamides, processes for the manufacture thereof, and fungicides containing these compounds.

The present invention relates to new and valuable substitutedcyanamides, processes for the manufacture thereof, and fungicidescontaining these compounds.

U.S. Pat. No. 3,954,992 discloses that cyanacetamide derivatives, e.g.,2-cyano-N-(ethylaminocarbonyl)-2-methoxyiminoacetamide, have afungicidal action on lower fungi. The use ofN-trichloromethylthiotetrahydrophthalimide for combating fungi has alsobeen disclosed (Chemical Week, June 21, 1972, p. 46).

We have found that substituted cyanamides of the formula ##STR1## whereR¹ denotes C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, R² denotes hydrogen, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy or halogen, R³ denotes hydrogen, C₁ -C₄ -alkyl orhalogen, R⁴ denotes C₁ -C₆ -alkoxycarbonyl, C₃ -C₄ -alkenoxycarbonyl, C₁-C₆ -alkylthiocarbonyl, or cyano, and R⁵ denotes C₁ -C₆ -alkyl which isunsubstituted or substituted by lower alkoxy, alkylthio, cyano or byhalogen; unsubstituted or halogen-substituted C₂ -C₅ -alkenyl; C₂ -C₄-alkynyl; C₃ -C₇ -cycloalkyl; a heterocyclic radical which isunsubstituted or substituted by lower alkyl or halogen and whichcontains one oxygen, one sulfur or one nitrogen atom, or up to twonitrogen atoms and one oxygen atom, or up to two nitrogen atoms and onesulfur atom; or R⁵ denotes unsubstituted phenyl or phenyl substituted byfrom one to three identical or different substituents selected from thegroup consisting of fluorine, chlorine, bromine, trifluoromethyl, cyano,nitro, C₁ -C₄ -alkyl, and C₁ -C₄ -alkoxy, have a good fungicidal actionon phytopathogenic fungi.

We have further found that substituted cyanamides are obtained byreaction of an N-halomethylanilide of the formula ##STR2## where R¹, R²,R³ and R⁵ have the meanings given above and Hal denotes halogen,especially chlorine and bromine, with a cyanamide of the formula##STR3## where R⁴ has the above meanings and M denotes hydrogen, analkali metal or tetraalkylammonium, in the presence or absence of anacid binder and of a solvent inert to the reactants.

By alkyl and the alkyl moiety of alkoxy in radicals R¹, R², R³ , R⁴ andR⁵, we mean--depending on the number of carbon atoms specified--forexample the following groups: methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl, and isomersthereof.

As alkenyl, for instance vinyl, allyl, methallyl and pentenyls may beparticularly mentioned. As C₂ -C₄ -alkynyl, for example ethynyl,propargyl and but-2-ynyl may be particularly mentioned.

As cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl andcyclohexyl may be particularly singled out.

Examples of halogen are fluorine, chlorine and bromine.

Preferred heterocyclic radicals at R⁵ are 5- to 6-membered, e.g., furan,thiophene, oxazole, isoxazole, thiazole, oxadiazole, thiodiazole,tetrahydrofuran, 2,3-dihydropyran and pyridine, and are unsubstituted orsubstituted by methyl and/or halogen.

Particularly suitable examples of substituted phenyl for R⁵ aremonosubstituted phenyls, such as fluorophenyl, chlorophenyl,bromophenyl, trifluoromethylphenyl, tolyl, anisyl, and nitrophenyl; anddisubstituted phenyls, such as dichlorophenyl, difluorophenyl,fluorochlorophenyl, dimethylphenyl, dimethoxyphenyl, methylfluorophenyl,methylchlorophenyl, methylbromophenyl, methoxychlorophenyl,methyltrifluoromethylphenyl, and chlorotrifluoromethylphenyl.

The reactions can be carried out in the presence or absence of solventsinert to the reactants. Examples of suitable solvents are aromatichydrocarbons, such as toluene and xylene; halogenated hydrocarbons, suchas chlorobenzene, chloroform, methylene chloride and methyl chloride;ethers, such as tetrahydrofuran and dioxane; nitriles, such asacetonitrile; N,N-dialkylamides, such as dimethylformamide; sulfones,such as dimethyl sulfoxide; ketones, such as acetone; aliphatic esters,such as ethyl acetate; and mixtures of these solvents. The reactiontemperature is from 0° to 150° C., preferably from 20° to 100° C.

If a cyanamide of the formula III in which M denotes hydrogen isreacted, it is advantageous to use an acid binder. Suitable binders aretertiary amines, e.g., triethylamine, pyridine and substitutedpyridines, and inorganic bases, e.g., oxides, hydroxides, carbonates andbicarbonates of alkali metals.

We have further found a special method for the manufacture of cyanamidecompounds of the formula I, wherein an N-halomethylanilide of theformula ##STR4## where R¹, R², R³ and R⁵ have the above meanings and Haldenotes chlorine or bromine, is reacted with a cyanamide of the formula##STR5## where R⁴ has the above meanings and M denotes an alkali metal,in a two-phase system (the one phase being water and the other a solventimmiscible with the aqueous phase and inert to the reactants) and in thepresence of a phase transfer catalyst. If desired, the reaction may alsobe carried out in a two-phase system in the presence of a phase transfercatalyst without the addition of water--the cyanamide of the formula IIIis then suspended as solid phase in the water-immiscible solvent.

The water-immiscible solvent is preferably an aromatic or a halogenatedhydrocarbon. The phase transfer catalyst is employed for instance inamounts of from 0.5 to 30 mole%, based on N-halomethylanilide of theformula II used.

The reaction is carried out at from 0° to 100° C., preferably from 10°to 50° C.

Suitable phase transfer catalysts are onium compounds, e.g., quaternaryammonium and phosphonium compounds, and macrocyclic polyethers. Examplesof quaternary ammonium compounds are tetrabutylammonium bisulfate,tetrapentylammonium chloride, tetraoctylammonium chloride,tripropylbutylammonium chloride, tricaprylylmethylammonium chloride,hexadecyl-trimethylammonium chloride, distearyl-dimethylammoniumchloride, dibenzyldimethylammonium methyl sulfate,dimethyldodecyl-benzylammonium chloride, benzyltrimethylammoniumchloride, benzyltriethylammonium chloride, and2-hydroxyethyltrimethylammonium chloride; examples of quaternaryphosphonium compounds are tributylmethylphosphonium bromide,hexadecyl-tributylphosphonium bromide, ethyltriphenylphosphoniumbromide, tetraphenylphosphonium bromide, and the hydroxides of theseonium compounds.

Examples of macrocyclic polyethers are 15-crown-5, 18-crown-6,dibenzo-18-crown-6 and dicyclohexyl-18-crown-6 (crown ethers).

To prepare the new compounds, at least 1 mole of cyanamide of theformula III is used per mole of N-halomethylanilide of the formula II.

To isolate the compounds of the formula I, for instance the halide whichhas formed is if desired filtered off, the filtrate is evaporated andthe residue is dissolved in an organic water-immiscible solvent. Theorganic phase is then washed with water, dried and concentrated invacuo. The product of the formula I which is obtained is in many casespure; if necessary, it can be further purified by recrystallization orchromatography, for example with silica gel.

In the two-phase manufacturing process, the organic phase is separated(or the undissolved material is filtered off) after completion of thereaction, washed with water and dried, and the active ingredient of theformula I is isolated as described above.

Some of the N-halomethylanilides used as starting materials are known(U.S. Pat. No. 3,637,847); others may be prepared in conventional mannerby reaction of correspondingly substituted phenylazomethines with acidchlorides of the formula R⁵ -CO-Hal, R⁵ having the above meanings andHal denoting halogen.

The cyanamide compounds of the formula III are known, for examplecyanocarbamic acid esters (German 2,474,453, German Laid-OpenApplication DE-OS 1,795,849), cyanocarbamic acid thiol esters (YukiCosei Kagaku Kyokai Shi, 1971, 29, (1) 67 (CA: 74, 140877 u)) anddicyanimide (Liebigs Ann. Chem., 427, 1, 1922; J. Chem. Soc., C, 1970,875).

Individual examples of cyanamide compounds, and salts thereof, suitableas starting products are as follows:

cyanocarbamic acid methyl ester and its sodium, potassium andtetramethylammonium salts;

cyanocarbamic acid ethyl ester and its sodium, potassium andtetramethylammonium salts;

cyanocarbamic acid n-propyl ester and its sodium, potassium, andtetramethylammonium salts;

cyanocarbamic acid isopropyl ester and its sodium and potassium salts;

cyanocarbamic acid n-butyl ester and its sodium and potassium salts;

cyanocarbamic acid sec-butyl ester and its sodium and potassium salts;

cyanocarbamic acid n-hexyl ester and its sodium and potassium salts;

cyanocarbamic acid methylthiol ester and its sodium, potassium andtetramethylammonium salts;

cyanocarbamic acid ethylthiol ester and its sodium, potassium andtetraethylammonium salts;

cyanocarbamic acid n-propylthiol ester and its sodium and potassiumsalts;

cyanocarbamic acid isopropylthiol ester and its sodium and potassiumsalts; and

dicyanimide; especially its sodium, potassium and tetramethylammoniumsalts.

The following examples illustrate the preparation of the new cyanamidecompounds of the formula I and of the starting materials of the formulaII.

In the examples, parts by weight bear the same relationship to parts byvolume as kilograms to liters.

EXAMPLE A

At 5° to 10° C. and while stirring, 315 parts by volume of a toluenesolution containing 1 mole of 2,6-dimethylphenylazomethine (U.S. Pat.No. 3,637,847) was dripped, with cooling, into a solution of 130.5 partsby weight of 2-furancarboxylic acid chloride in 100 parts by volume oftoluene; the mixture was then stirred for 10 hours at room temperature.After cooling, filtration and drying in vacuo, there was obtained 198parts by weight of N-chloromethylfuran-2-carboxylicacid-2',6'-dimethylanilide of melting point 124°-126° C.

The following N-halomethylanilides of the formula II may be preparedanalogously:

    ______________________________________                                         ##STR6##                                                                                                             m.p.                                  R.sup.1                                                                            R.sup.2                                                                              R.sup.3  Hal  R.sup.5       °C.                            ______________________________________                                        CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CH.sub.3      solid                                                                         mass                                  CH.sub.3                                                                           C.sub.2 H.sub.5                                                                      H        Cl   CH.sub.3      solid                                                                         mass                                  C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      H        Cl   CH.sub.3      oil                                   CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   C.sub.2 H.sub.5                                                                             oil                                   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                      H        Cl   C.sub.2 H.sub.5                                                                             oil                                   C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      H        Cl   C.sub.2 H.sub.5                                                                             oil                                   CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CH(CH.sub.3).sub.2                                  CH.sub.3                                                                           C.sub.2 H.sub.5                                                                      H        Cl   CH(CH.sub.3).sub.2                                  C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      H        Cl   CH(CH.sub.3).sub.2                                                                          75-76                                 C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      H        Cl   C(CH.sub.3 ).sub.3                                                                          oil                                   CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CH(Cl)CH.sub.3                                                                              95                                    C.sub.2 H.sub.5                                                                    CH.sub.3                                                                             H        Cl   CH(Cl)CH.sub.3                                      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      H        Cl   CH(Cl)CH.sub.3                                      CH.sub.3                                                                           CH.sub.3                                                                             2-CH.sub. 3                                                                            Cl   CH(Cl)CH.sub.3                                      CH.sub.3                                                                           C.sub.2 H.sub.5                                                                      H        Cl   CH.sub.2CH.sub.2 Cl                                                                         viscous                                                                       oil                                   CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CH.sub.2CH.sub.2 Cl                                 CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CH.sub.2CH.sub.2CH.sub.2 Cl                         CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CHCl.sub.2    102-104                               CH.sub.3                                                                           CH.sub.3                                                                             CH.sub.3 Cl   CHCl.sub.2                                          CH.sub.3                                                                           C.sub.2 H.sub.5                                                                      H        Cl   CHCl.sub.2    88-90                                 CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CCl.sub.3     oil                                   CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CHCH.sub.2                                          CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR7##                                           CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR8##     91-92                                 CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR9##                                           CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CHCCl.sub.2                                         CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CCLCCL.sub.2                                        CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR10##    82                                    CH.sub.3                                                                           C.sub.2 H.sub.5                                                                      H        Cl                                                                                  ##STR11##    oil                                   C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      H        Cl                                                                                  ##STR12##    oil                                   CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR13##                                          CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR14##                                          CH.sub.3                                                                           C.sub.2 H.sub.5                                                                      H        Cl                                                                                  ##STR15##                                          C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      H        Cl                                                                                  ##STR16##    97-100                                CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CH.sub.2 OCH.sub.3                                                                          70                                    CH.sub.3                                                                           CH.sub.3                                                                             CH.sub.3 Cl   CH.sub.2 OCH.sub.3                                  CH.sub.3                                                                           C.sub.2 H.sub.5                                                                      H        Cl   CH.sub.2 OCH.sub.3                                  C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      H        Cl   CH.sub.2 OCH.sub.3                                                                          oil                                   CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CH.sub.2 SCH.sub.3                                                                          cryst-                                                                        alline                                                                        mass                                  CH.sub.3                                                                           C.sub.2 H.sub.5                                                                      H        Cl   CH.sub.2 SCH.sub.3                                                                          127                                   C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      H        Cl   CH.sub.2 SCH.sub.3                                                                          oil                                   CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CH.sub.2CN                                          CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR17##    133                                   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                      H        Cl                                                                                  ##STR18##                                          C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      H        Cl                                                                                  ##STR19##    98-99                                 CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR20##    86-88                                 CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR21##    114-116                               CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR22##    141-143                               CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR23##    93                                    CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR24##    145                                   CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR25##    120                                   CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR26##    108                                   C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      H        Cl                                                                                  ##STR27##                                          CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR28##    132                                   CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR29##                                          C.sub. H.sub.5                                                                     C.sub.2 H.sub.5                                                                      H        Cl                                                                                  ##STR30##    63-64                                 CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR31##    108-109                               C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      H        Cl                                                                                  ##STR32##    112-114                               CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR33##    118-119                               CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR34##    119-120                               CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR35##                                          CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR36##    205- 207                              CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR37##    152-154                               CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR38##                                          CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR39##    94-97                                 CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR40##    120-121                               CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR41##                                          CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR42##    118                                   CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR43##    124-126                               CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR44##                                          C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      H        Cl                                                                                  ##STR45##    69-70                                 CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR46##    68-70                                 C.sub.2 H.sub.5                                                                    C.sub. 2 H.sub.5                                                                     H        Cl                                                                                  ##STR47##                                          CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR48##                                          CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR49##                                          CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR50##    83-85                                 CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR51##    106                                   CH.sub.3                                                                           CH.sub.3                                                                             H                                                                                            ##STR52##                                          CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR53##    92-93                                 CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR54##    107-108                               CH.sub.3                                                                           CH.sub.3                                                                             H        Cl                                                                                  ##STR55##    105                                   CH.sub. 3                                                                          CH.sub.3                                                                             H        Cl                                                                                  ##STR56##    118-120                               C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      H        Cl                                                                                  ##STR57##    118-120                               CH.sub.3                                                                           H      4-Cl     Cl   CH.sub.2 OCH.sub.3                                                                          oil                                   CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CH.sub.2 OC.sub.2 H.sub.5                                                                   80-81                                 CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CH.sub.2CH.sub.2 OCH.sub.3                                                                  oil                                   CH.sub.3                                                                           CH.sub.3                                                                             H        Cl   CH(CH.sub.3)OCH.sub.3                                                                       oil                                   ______________________________________                                    

EXAMPLE 1

A mixture of 29.2 parts by weight of N-chloromethylfuran-2-carboxylicacid-2',6'-diethylanilide and 13.4 parts by weight of the sodium salt ofcyanocarbamic acid methyl ester in 120 parts by volume of acetonitrileis stirred for 12 hours at 25° C. After evaporation of the solvent invacuo, the solvent is dissolved in ethyl acetate and water. The organicphase is dried, the solvent is evaporated, and the residue is trituratedwith diisopropyl ether; there is obtained 25.5 parts ofN-methoxycarbonyl-N-(N'-furyl-2-carbonyl,N'-2',6'-diethylanilinomethyl)-cyanamide of melting point 101°-103° C.

EXAMPLE 2

At 20° to 25° C., a solution of 26.4 parts by weight ofN-(chloromethyl)-furan-2-carboxylic acid-2',6'-dimethylanilide in 70parts by volume of methylene chloride is dripped, with intensive mixingof the phases, into a solution of 12.2 parts by weight of the sodiumsalt of cyanocarbamic acid methyl ester and 1 part ofbenzyltriethylammonium chloride in 30 parts by volume of water. Aftermixing for 6 hours, the organic phase is separated, washed 3 times withwater and dried over sodium sulfate. After evaporation of the solventthere is obtained 29.0 parts by weight ofN-methoxycarbonyl-N-(N'-furyl-2-carbonyl,N'-2',6'-dimethylanilinomethyl)-cyanamide; after recrystallization froma small amount of methanol, the compound has a melting point of 96°-98°C.

EXAMPLE 3

24.1 parts by weight of N-chloromethylbenzoic acid-2,6-dimethylanilideis dissolved in 100 parts by volume of acetonitrile; 11.8 parts byweight of the sodium salt of cyanocarbamic acid methyl ester is added,and the mixture is stirred at 25° C. for 24 hours. Undissolved matter isfiltered off, the filtrate is concentrated in vacuo and the residue isdissolved in methylene chloride and water. The solvent is evaporatedfrom the organic phase and the residue is recrystallized from methanol(100 ml). There is obtained 18.0 parts by weight ofN-methoxycarbonyl-N-(N'-benzoyl,N'-2',6'-dimethylanilinomethyl)-cyanamide of melting point 136° C.

The following compounds are obtained analogously:

    __________________________________________________________________________     ##STR58##                                                                                                            m.p.                                                                          (°C.)                          Compound                                or                                    no.   R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                             R.sup.4   R.sup.5     n.sub.D.sup.20                        __________________________________________________________________________    1     CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       CH.sub.3    112-114                               2     CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 C.sub.2 H.sub.5                                                                CH.sub.3    78-80                                 3     CH.sub.3                                                                         C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                       CH.sub.3                                          4     CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                   5     CH.sub.3                                                                         C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                   6     C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                   7     CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       CH(CH.sub.3).sub.2                                8     C.sub. 2 H.sub.5                                                                 C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                       CH(CH.sub.3).sub.2                                                                        1.516                                 9     CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       CH(Cl)CH.sub.3                                                                            100                                   10    CH.sub.3                                                                         C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                       CH(Cl)CH.sub.3                                    11    CH.sub.3                                                                         CH.sub.3                                                                         H     COSCH.sub.3                                                                             CH(Cl)CH.sub.3                                    12    CH.sub.3                                                                         CH.sub.3                                                                         H     CN        CH(Cl)CH.sub.3                                    13    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       CH.sub.2CH.sub.2 Cl                                                                       oil                                   14    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       CH.sub.2CH.sub.2CH.sub.2 Cl                       15    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       CHCl.sub.2                                        16    CH.sub.3                                                                         C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                       CHCl.sub.2                                        17    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 C.sub.2 H.sub.5                                                                CHCl.sub.2                                        18    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 i-C.sub.3 H.sub.7                                                              CHCl.sub.2                                        19    CH.sub.3                                                                         CH.sub.3                                                                         H     COSCH.sub.3                                                                             CHCl.sub.2                                        20    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.2                                                                       CCl.sub.3                                         21    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       CHCH.sub.2  92                                    22    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR59##                                        23    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR60##  90                                    24    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR61##                                        25    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       CHCCl.sub.2                                       26    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 C.sub.2 H.sub.5                                                                CClCCl.sub.2                                      27    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR62##  106                                   28    CH.sub.3                                                                         C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                        ##STR63##                                        29    C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                        ##STR64##                                        30    CH.sub.3                                                                         H  3-CH.sub.3                                                                          CO.sub.2 C.sub.2 H.sub.5                                                                 ##STR65##                                        31    CH.sub.3                                                                         H  5-CH.sub.3                                                                          CO.sub.2 C.sub.2 H.sub.5                                                                 ##STR66##                                        32    CH.sub.3                                                                         H  5-Cl  CO.sub.2 CH.sub.3                                                                        ##STR67##                                        33    CH.sub.3                                                                         CH.sub.3                                                                         H     COSCH.sub.3                                                                              ##STR68##                                        34    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR69##                                        35    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR70##                                        36    C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                        ##STR71##  viscous                               37    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       CH.sub.2 OCH.sub.3                                                                        74-76                                 38    CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                          CO.sub.2 CH.sub.3                                                                       CH.sub.2 OCH.sub.3                                39    C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                       CH.sub.2 OCH.sub.3                                40    CH.sub.3                                                                         CH.sub.3                                                                         H     CN        CH.sub.2 OCH.sub.3                                41    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 C.sub.2 H.sub.5                                                                CH.sub.2 OCH.sub.3                                                                        86                                    42    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 i-C.sub.3 H.sub.7                                                              CH.sub.2 OCH.sub.3                                43    CH.sub.3                                                                         CH.sub.3                                                                         H     COSCH.sub.3                                                                             CH.sub.2 OCH.sub.3                                                                        118                                   44    CH.sub.3                                                                         H  5-CH.sub.3                                                                          CO.sub.2 CH.sub.3                                                                       CH.sub.2 OCH.sub.3                                45    CH.sub.3                                                                         H  4-Cl  CO.sub.2 CH.sub.3                                                                       CH.sub.2 OCH.sub.3                                                                        103                                   46    CH.sub.3                                                                         H  4-CH.sub.3 O                                                                        CO.sub.2 CH.sub.3                                                                       CH.sub.2 OCH.sub.3                                47    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       CH.sub.2 SCH.sub.3                                48    CH.sub.3                                                                         C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                       CH.sub.2 SCH.sub.3                                49    C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                       CH.sub.2 SCH.sub.3                                50    CH.sub.3                                                                         CH.sub.3                                                                         H     COSCH.sub.3                                                                             CH.sub.2 SCH.sub.3                                51    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       CH.sub.2CN                                        52    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR72##                                        53    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR73##  136                                   54    CH.sub.3                                                                         CH.sub.3                                                                         H     CN                                                                                       ##STR74##                                        55    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR75##  117                                   56    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR76##  145                                   57    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR77##  oil                                   58    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR78##  98-101                                59    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR79##  161                                   60    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR80##  90                                    61    CH.sub.3                                                                         H  5-CH.sub.3                                                                          CO.sub.2 CH.sub.3                                                                        ##STR81##                                        62    CH.sub.3                                                                         CH.sub.3                                                                         H     COSCH.sub.3                                                                              ##STR82##                                        63    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR83##  139                                   64    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR84##                                        65    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR85##                                        66    C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                        ##STR86##                                        67    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR87##  105-106                               68    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR88##  125-127                               69    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR89##  117-119                               70    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR90##                                        71    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR91##                                        72    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR92##  132-133                               73    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR93##                                        74    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR94##  115-116                               75    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 C.sub.2 H.sub.5                                                                 ##STR95##                                        76    CH.sub.3                                                                         C.sub.2 H.sub.5                                                                  H     CO.sub.2 C.sub.2 H.sub.5                                                                 ##STR96##                                        77    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR97##  121                                   78    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR98##                                        79    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR99##  130-132                               80    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR100## 96-98                                 81    CH.sub.3                                                                         C.sub.2 H.sub.5                                                                  H     CO.sub.2 C.sub.2 H.sub.5                                                                 ##STR101## oil                                   82    CH.sub.3                                                                         CH.sub.3                                                                         H     COSCH.sub.3                                                                              ##STR102## 121                                   83    CH.sub.3                                                                         CH.sub.3                                                                         H     CN                                                                                       ##STR103##                                       84    CH.sub.3                                                                         H  5-CH.sub.3                                                                          CO.sub.2 CH.sub.3                                                                        ##STR104##                                       85    C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                        ##STR105## 101-103                               86    CH.sub. 3                                                                        CH.sub.3                                                                         CH.sub.3                                                                            CO.sub.2 CH.sub.3                                                                        ##STR106##                                       87    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 C.sub.2 H.sub.5                                                                 ##STR107## oil                                   88    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 i-C.sub.3 H.sub.7                                                               ##STR108##                                       89    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR109##                                       90    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR110## 126-128                               91    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR111##                                       92    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR112##                                       93    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR113## 122                                   94    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR114## 106-108                               95    CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR115##                                       96    CH.sub.3                                                                         H  4-Cl  CO.sub.2 CH.sub.3                                                                        ##STR116##                                       97    CH.sub.3                                                                         H  H     CO.sub.2 CH.sub.3                                                                        ##STR117##                                       98    H  CH.sub.3                                                                         3-Cl  CO.sub.2 CH.sub.3                                                                        ##STR118##                                       99    H  Cl H     CO.sub.2 CH.sub.3                                                                        ##STR119##                                       100   CH.sub.3                                                                         H  5-Cl  CO.sub.2 CH.sub.3                                                                       CH.sub.2 OCH.sub.3                                                                        95                                    101   CH.sub.3                                                                         H  H     CO.sub.2 CH.sub.3                                                                       CH.sub.2 OCH.sub.3                                                                        90                                    102   H  Cl H     CO.sub.2 CH.sub.3                                                                       CH.sub.2 OCH.sub.3                                103   CH.sub.3                                                                         C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                       CH.sub.2 OCH.sub.3                                                                        1.5261                                104   CH.sub.3                                                                         C.sub.2 H.sub.5                                                                  H     CO.sub.2 C.sub.2 H.sub.5                                                                CH.sub.2 OCH.sub.3                                                                        1.5210                                105   CH.sub.3                                                                         CH.sub. 3                                                                        4-t . C.sub.4 H.sub.9                                                               CO.sub.2 CH.sub.3                                                                       CH.sub.2 OCH.sub.3                                                                        98                                    106   CH.sub.3                                                                         H  5-t . C.sub.4 H.sub.9                                                               CO.sub.2 CH.sub.3                                                                       CH.sub.2 OCH.sub.3                                                                        1.5130                                107   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       CH.sub.2CH.sub.2 OCH.sub.3                                                                oil                                   108   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 C.sub.2 H.sub.5                                                                CH.sub.2CH.sub.2 OCH.sub.3                                                                oil                                   109   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       CH(CH.sub.3)OCH.sub.3                                                                     oil                                   110   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 C.sub.2 H.sub.5                                                                CH(CH.sub.3)OCH.sub.3                                                                     84-86                                 111   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.2 CHCH.sub.2                                                            CH.sub.2 OCH.sub.3                                                                        oil                                   112   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.2 CHCH.sub.2                                                             ##STR120##                                       113   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       CH.sub.2 Cl 125-128                               114   CH.sub.3                                                                         C.sub.2 H.sub.5                                                                  H     CO.sub.2 CH.sub.3                                                                       CH.sub.2 Cl 61-63                                 115   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 C.sub.2 H.sub.5                                                                CH.sub.2 Cl 93-95                                 116   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub. 2 CH.sub.3                                                                      CH.sub.2CH.sub.2F                                 117   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR121##                                       118   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR122##                                       119   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR123##                                       120   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR124##                                       121   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR125##                                       122   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR126## 143-144                               123   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 C.sub.2 H.sub.5                                                                 ##STR127## 110                                   124   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR128## 136                                   125   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 C.sub.2 H.sub.5                                                                 ##STR129## 123-124                               126   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 C.sub.2 H.sub.5                                                                 ##STR130## 95-97                                 127   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 C.sub.2 H.sub.5                                                                 ##STR131## 193                                   128   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR132## 102-104                               129   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR133## 105-106                               130   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR134## 108-109                               131   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR135## 145-147                               132   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                       CH.sub.2 OC.sub.2 H.sub.5                                                                 76-78                                 133   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 C.sub.2 H.sub.5                                                                CH.sub.2 OC.sub.2 H.sub.5                                                                 79                                    134   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR136## oil                                   135   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 C.sub.2 H.sub.5                                                                 ##STR137## 64-68                                 136   CH.sub.3                                                                         CH.sub.3                                                                         H     CO.sub.2 CH.sub.3                                                                        ##STR138## 99                                    __________________________________________________________________________

The new active ingredients are applied for instance in the form ofdirectly sprayable solutions, powders, suspensions (includinghigh-percentage aqueous, oily or other suspensions or dispersions),emulsions, oil dispersions, pastes, dusts, broadcasting agents, orgranules by spraying, atomizing, dusting, broadcasting or watering. Theforms of application depend entirely on the purpose for which the agentsare being used; in any case they should ensure a fine distribution ofthe active ingredient.

For the preparation of solutions, emulsions, pastes and oil dispersionsto be sprayed direct, mineral oil fractions of medium to high boilingpoint, such as kerosene or diesel oil, further coal-tar oils, and oilsof vegetable or animal origin, aliphatic, cyclic and aromatichydrocarbons such as benzene, toluene, xylene, paraffin,tetrahydronaphthalene, alkylated naphthalenes and their derivatives suchas methanol, ethanol, propanol, butanol, chloroform, carbontetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone,etc., and strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes,oil dispersions or wettable powders by adding water. To prepareemulsions, pastes and oil dispersions the ingredients as such ordissolved in an oil or solvent may be homogenized in water by means ofwetting or dispersing agents, adherents or emulsifiers. Concentrateswhich are suitable for dilution with water may be prepared from activeingredient, wetting agent, adherent, emulsifying or dispersing agent andpossibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal andammonium salts of ligninsulfonic acid, naphthalenesulfonic acids,phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkylsulfonates, alkali metal and alkaline earth metal salts ofdibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcoholsulfates, alkali metal and alkaline earth metal salts of fatty acids,salts of sulfated hexadecanols, heptadecanols, and octadecanols, saltsof sulfated fatty alcohol glycol ethers, condensation products ofsulfonated naphthalene and naphthalene derivatives with formaldehyde,condensation products of naphthalene or naphthalenesulfonic acids withphenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcoholethylene oxide condensates, ethoxylated castor oil, polyoxyethylenealkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycolether acetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powders, dusts and broadcasting agents may be prepared by mixing orgrinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may beprepared by bonding the active ingredients to solid carriers. Examplesof solid carriers are mineral earths such as silicic acid, silica gels,silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess,clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,magnesium oxide, ground plastics, fertilizers such as ammonium sulfate,ammonium phosphate, ammonium nitrate, and ureas, and vegetable productssuch as grain flours, bark meal, wood meal, and nutshell meal,cellulosic powders, etc.

The new active ingredients have a strong fungitoxic action onphytopathogenic fungi, especially from the Phycomycetes class. The newcompounds are therefore suitable for instance for combating Phytophthorainfestans in tomatoes and potatoes, Phytophthora parasitica instrawberries, Phytophthora cyctorum in apples, Pseudoperonosporacubensis in cucumbers, Pseudoperonospora humuli in hops, Peronosporadestructor in onions, Peronospora sparsa in roses, Peronospora tabacinain tobacco, Plasmopara viticola in grapes, Plasmopara halstedii insunflowers, Sclerospora macrospora in Indian corn, Bremia lactucae inlettuce, Mucor mucedo in fruit, and Rhizopus nigricans in beets. Thefungicidal agents contain from 0.1 to 95 wt% of active ingredient,preferably from 0.5 to 90%. The application rates depend on the type ofeffect desired and are from 0.1 to 5 kg of active ingredient perhectare. Some of the active ingredients have curative properties, i.e.,the agents may also be applied after the plants have been infected bythe pathogen, and success is still ensured. Furthermore, many of the newcompounds have a systemic action, which means that visible plant partsmay also be protected by a root treatment.

The new compounds may also be used to combat fungi which cause seedlingand emergence diseases, e.g., Pythium and Aphanomyces species inLeguminosae and cotton. For this use, the active ingredients are appliedas seed disinfectants at rates of from 10 to 200 g of active ingredientper 100 kg of seed.

The agents according to the invention may also be mixed and applied withother active ingredients, e.g., herbicides, insecticides, growthregulators, other fungicides and fertilizers. When mixed with otherfungicides, the spectrum of fungicidal action is in many casesincreased; with a number of these fungicidal compositions, synergisticeffects also occur; i.e., the fungicidal action of the combinationproduct is greater than the effect of the individual components addedtogether. The spectrum of action is particularly favorably influencedwhen the compounds according to the invention are mixed with thefollowing fungicides:

manganese N,N-ethylene-bis-dithiocarbamate,

manganese zinc N,N-ethylenediamine-bis-dithiocarbamate,

the ammonia complex of zinc N,N-ethylene-bis-dithiocarbamate andN,N'-polyethylene- bis (thiocarbamoyl)-disulfide,

N-trichloromethylthiotetrahydrophthalimide,N-trichloromethylphthalimide,5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,

2-methoxycarbonylaminobenzimidazole, 2-thiocyanomethylthiobenzothiazole,1,4-dichloro-2,5-dimethoxybenzene,2,3-dichloro-6-methyl-1,4-oxathiin-5-carboxylic acid anilide,2-methyl-5,6-dihydro-4H-pyran-3-carboxylic acid anilide,2,4,5-trimethylfuran-3-carboxylic acid anilide,2-methylfuran-3-carboxylic acid anilide, 2,5-dimethylfuran-3-carboxylicacid cyclohexylamide,N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxylic acid amide,5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine, and5-methyl-5-methoxymethyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine-N-p-fluorophenyl-2,3-di-chloromaleimide.

The following lists of fungicides with which the compounds according tothe invention may be combined is intended to illustrate and not restrictthe combination possibilities.

Examples of fungicides which may be combined with the compoundsaccording to the invention are: dithiocarbamates and their derivatives,e.g. iron(III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate,zinc N,N-ethylene-bis-dithiocarbamate, tetramethylthiuram disulfide,zinc N,N'-propylene-bis-dithiocarbamate, and the ammonia complex of zincN,N'-propylene-bis-dithiocarbamate andN,N'-polypropylene-bis-(thiocarbamoyl)-disulfide; nitro derivatives,e.g. dinitro-(1-methylheptyl)-phenyl crotonate,2-sec.-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate and2-sec.-butyl-4,6-dinitrophenyl isopropyl carbonate; heterocycliccompounds, e.g. 2-heptadecyl-2-imidazoline acetate,2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethylphthalimidophosphonothioate,5-amino-1-(bis-(dimethylamino)-phosphinyl)-3-phenyl-1,2,4-triazole,2,3-dicyano-1,4-dithiaanthraquinone,2-thio-1,3-dithio(4,5-b)-quinoxaline, methyl1-(butylcarbamoyl)-2-benzimidazole-carbamate,4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,pyridine-2-thio-1-oxide, 8-hydroxyquinoline and its copper salt,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide,2,3-dihydro-5-carboxanildio-6-methyl-1,4-oxathiin,2-fur-2-yl-benzimidazole,piperazine-1,4-diyl-bis-(1-(2,2,2-trichloroethyl)-formamide),2-thiazol-4-yl-benzimidazole,5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine,bis-(p-chlorophenyl)-3-pyridinemethanol,1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene,1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene and various fungicides,e.g. dodecylguanidine acetate,3-(2-(3,5-dimethyl-2-hydroxycyclohexyl)-2-hydroxyethyl)-glutarimide,hexachlorobenzene,N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenyl-sulfuric aciddiamide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2-methyl-benzoicacid anilide, 2-iodo-benzoic acid anilide,1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,2,6-dimethyl-N-tridecylmorpholine and its salts,2,6-dimethyl-N-cyclododecyl-morpholine and its salts,α-(2-chlorophenyl-α-(4-chlorophenyl)-5-pyrimidine-methanol,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone,and1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol.

The following examples illustrate the fungicidal action of thecompounds. The following prior art fungicidal compounds are used in theexamples for comparison purposes: ##STR139##

EXAMPLE 4 Fungicidal action on Phytophthora infestans in tomatoes

Leaves of tomato plants of the "Professor Rudloff" variety are sprayedwith aqueous suspensions containing (dry basis) 80% (wt%) of activeingredient and 20% of sodium lignin sulfonate. 0.025 and 0.012% (drybasis) spray liquors are used. After the sprayed-on layer has dried, theleaves are infected with a zoospore suspension of Phytophthorainfestans. The plants are then placed for 5 days in a steam-saturated(moist) chamber kept at 16° to 18° C. After this period, the disease hasspread on the untreated control plants to such an extent that thefungicidal action of the compounds can be assessed.

    ______________________________________                                                    Leaf attack after spraying with liquor                            Active      containing active ingredients in amounts of                       ingredient  0.025%         0.012%                                             ______________________________________                                        37          0              1                                                  56          0              0                                                  74          0              0                                                  80          0              1                                                  A (prior art)                                                                             2              1                                                  Control (untreated)                                                                       5                                                                 ______________________________________                                         0 = no fungus attack, graduated down to 5 = total attack                 

EXAMPLE 5 Fungicidal action on Plasmopara viticola in grapes

Leaves of potted vines of the Muller-Thurgau variety are infected with azoospore suspension of Plasmopara viticola. The plants are then placedfor 16 hours in a steam-saturated (moist) chamber at 24° C. The leaftissue is infected during this period. To determine the curative action,the plants are then sprayed with aqueous suspensions containing (drybasis) 80% (by weight) of the active ingredient and 20% of sodium ligninsulfonate. 0.05% spray liquors (dry basis) are used. The vines are thenplaced for 8 days in the greenhouse at 22° to 24° C. To accelerate andintensify the sporangiophore discharge, the plants are then again placedin the moist chamber for 16 hours. Leaf attack is then assessed asfollows: 0=no damage, graduated down to 5=total attack (control).

    ______________________________________                                                   Leaf attack after spraying with liquor                                        containing active ingredients in an                                           amount of                                                          After ingredient           0.05%                                              ______________________________________                                         1                         0                                                   8                         0                                                   9                         0                                                  27                         0                                                  36                         0                                                  37                         0                                                  53                         0                                                  80                         0                                                  85                         0                                                  A (prior art)              2-3                                                Control (untreated)                                                                        5                                                                ______________________________________                                    

EXAMPLE 6 Fungicidal action on emergence diseases in peas

100 g samples of pea seeds of the "Senator" variety are carefully shakenfor about 5 minutes in glass bottles with 300 mg (=0.3 wt%) of seeddisinfectant formulations containing (dry basis) 40% of activeingredient and 60% of clay. Subsequently, 100 seeds are sown 3 cm deepand 3 to 5 cm apart in seed boxes in a compost naturally and heavilyinfested with the fungi Pythium spec., Aphanomyces spec. and Fusariumoxysporum. The boxes are set up in the greenhouse at from 17° to 20° C.The number of healthy pea plants is determined after 21 days.

    ______________________________________                                                          Percentage of healthy                                                         plants after 21 days in                                     After ingredient  compost                                                     ______________________________________                                        74                90                                                          B (prior art)     60                                                          Control (untreated)                                                                             10                                                          Control (sterilized compost)                                                                    93                                                          ______________________________________                                    

EXAMPLE 7

90 parts by weight of compound 1 is mixed with 10 parts by weight ofN-methyl-α-pyrrolidone. A mixture is obtained which is suitable forapplication in the form of very fine drops.

EXAMPLE 8

20 parts by weight of compound 2 is dissolved in a mixture consisting of80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide,5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid,and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1mole of castor oil. By pouring the solution into 100,000 parts by weightof water and uniformly distributing it therein, an aqueous dispersion isobtained containing 0.02% by weight of the active ingredient.

EXAMPLE 9

20 parts by weight of compound 3 is dissolved in a mixture consisting of40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol,20 parts by weight of the adduct of 7 moles of ethylene oxide with 1mole of isooctylphenol, and 10 parts by weight of the adduct of 40 molesof ethylene oxide with 1 mole of castor oil. By pouring the solutioninto 100,000 parts by weight of water and finely distributing ittherein, an aqueous dispersion is obtained containing 0.02% by weight ofthe active ingredient.

EXAMPLE 10

20 parts by weight of compound 1 is dissolved in a mixture consisting of25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oilfraction having a boiling point between 210° and 280° C., and 10 partsby weight of the adduct of 40 moles of ethylene oxide with 1 mole ofcastor oil. By pouring the solution into 100,000 parts by weight ofwater and uniformly distributing it therein, an aqueous dispersion isobtained containing 0.02% by weight of the active ingredient.

EXAMPLE 11

20 parts by weight of compound 2 is well mixed with 3 parts by weight ofthe sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts byweight of the sodium salt of a lignin-sulfonic acid obtained from asulfite waste liquor, and 60 parts by weight of powdered silica gel, andtriturated in a hammer mill. By uniformly distributing the mixture in20,000 parts by weight of water, a spray liquor is obtained containing0.1% by weight of the active ingredient.

EXAMPLE 12

3 parts by weight of compound 3 is intimately mixed with 97 parts byweight of particulate kaolin. A dust is obtained containing 3% by weightof the active ingredient.

EXAMPLE 13

30 parts by weight of compound 4 is intimately mixed with a mixtureconsisting of 92 parts by weight of powdered silica gel and 8 parts byweight of paraffin oil which has been sprayed onto the surface of thissilica gel. A formulation of the active ingredient is obtained havinggood adherence.

EXAMPLE 14

40 parts by weight of compound 1 is intimately mixed with 10 parts ofthe sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2parts of silica gel and 48 parts of water to give a stable aqueousdispersion. Dilution in 100,000 parts by weight of water gives anaqueous dispersion containing 0.04 wt% of active ingredient.

EXAMPLE 15

20 parts of compound 2 is intimately mixed with 2 parts of the calciumsalt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcoholpolyglycol ether, 2 parts of the sodium salt of a phenolsulfonicacid-urea-formaldehyde condensate and 68 parts of a paraffinic mineraloil. A stable oily dispersion is obtained.

We claim:
 1. A substituted cyanamide of the formula ##STR140## where R¹denotes C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, R² denotes hydrogen, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy or halogen, R³ denotes hydrogen, C₁ -C₄ -alkyl orhalogen, R⁴ denotes C₁ -C₆ -alkoxycarbonyl, C₃ -C₄ -alkenoxycarbonyl, C₁-C₆ -alkylthiocarbonyl, or cyano, and R⁵ denotes C₁ -C₆ -alkyl which isunsubstituted or substituted by lower alkoxy, alkylthio, cyano or byhalogen; unsubstituted or halogen-substituted C₂ -C₅ -alkenyl; C₂ -C₄-alkynyl; C₃ -C₇ -cycloalkyl; or R⁵ denotes unsubstituted phenyl orphenyl substituted by from one to three identical or differentsubstituents selected from the group consisting of fluorine, chlorine,bromine, trifluoromethyl, cyano, nitro, C₁ -C₄ -alkyl, and C₁ -C₄-alkoxy.
 2. A substituted cyanamide selected from the group consistingof N-methoxycarbonyl-N-(N'-methoxyacetyl,N'-2',6'-dimethylanilinomethyl)-cyanamide,N-ethoxycarbonyl-N-(N'-methoxyacetyl,N'-2',6'-dimethylanilinomethyl)-cyanamide,N-methoxycarbonyl-N-(N'-3-fluorobenzoyl,N'-2',6'-dimethylanilinomethyl)-cyanamide andN-methoxycarbonyl-N-(N'-4-fluorobenzoyl,N'-2',6'-dimethylanilinomethyl)-cyanamide.
 3. A process for combatingfungi, which comprises treating the fungi or the objects to be protectedagainst fungus attack with an effectius amount of a substitutedcyanamide of the formula ##STR141## where R¹ denotes C₁ -C₄ -alkyl or C₁-C₄ -alkoxy, R² denotes hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy orhalogen, R³ denotes hydrogen, C₁ -C₄ -alkyl or halogen, R⁴ denotes C₁-C₆ -alkoxycarbonyl, C₃ -C₄ -alkenoxycarbonyl, C₁ -C₆-alkylthiocarbonyl, or cyano, and R⁵ denotes C₁ -C₆ -alkyl which isunsubstituted or substituted by lower alkoxy, alkylthio, cyano or byhalogen; unsubstituted or halogen-substituted C₂ -C₅ -alkenyl; C₂ -C₄-alkynyl; C₃ -C₇ -cycloalkyl; or R⁵ denotes unsubstituted phenyl orphenyl substituted by from one to three identical or differentsubstituents selected from the group consisting of fluorine, chlorine,bromine, trifluoromethyl, cyano, nitro, C₁ -C₄ -alkyl, and C₁ -C₄-alkoxy.